Water-insoluble azo dyestuffs and material dyed therewith



Patented May 19, 1931 l,806,tt7

are

RICHARD DERESER AND MOl-DmE'lKE, OF FRANKFORT-ON-THE-MAIN-HOCI-IST, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A

CORPORATION OF DE-LAFHARE WATER-INSOLUBLE AZO DYESTUFFS AND IIIATEREAL DYE-D THEREWITH No Drawing. Application filed December 5, 1928, Serial No. 324,051, and in Germany December 17, 1927.

OK? X wherein both the Xs stand for halogen but at least one of which must be a bro-mine atom and wherein the aryl residue may be substituted or'not but must not contain any free sulfonioor carboxylic groups.

The dyestuffs are insoluble in water possess a good fastness to light.

The following examples illustrate our invention but they are not intended to limit it thereto, the parts being parts by weight:

1. 50 g. of well boiled cotton yarn are treated with the grounding liquor for half an hour, well freed from water by wringing it out or by centrifugating it and dyed for one minute in the diazo solution. The dyed yarn is then thoroughly rinsed, soaped at boiling temperature and again rinsed.

The grounding liquor is prepared as follows:

and

of 2.3- hlydroxynaphthoic acid-2'.5-dimeth0xyl'- ice w r U! 1 liter.

The developing bath is prepared as follows:

of 4-chloro 5-hr0mo-2-amino-1-to1uene are made llllO a paste with 5.2 cc. of hydrochloric acid of 22 Be. and a small quantity of water;

1.44 g. of dissolved sodium nitrite and some ice are gradually added. After the diazotization is complete, the solution is neutralized with 4 g. of sodium acetate and the whole is made up to 1 liter.

The dyeing has a very vivid, bluish-red shade, very fast to light. The dyestuff has the formula:

OCH;

2. By substituting in the grounding liquor of the preceding example for the 2.3- hydroxynaplithoic acid-2C5 -dimethoXy-1- anilide the equimolecular quantity of 2.8-hydroxynaphthoic acid 2- or t-anisidide, there is also obtained a vivid bluish red shade of very good fastness to light. By using an equimolecular quantity of 2.3-hydroXynaphthoic acid-5-ohloro-2t-anisidide (NH: OCH (11 2: 1 5) for preparing the grounding liquor, there is obtained a dull alizarine red of very good fastness to light.

3. The grounding liquor isprepared as follows:

4.5 g. of 2.3-hydroxynaphthoic acid-5-chloro-2'-anisidide (NH: 0CH C1=2 l 5) cc. of. sodium Turkey red oil of 50% strength and cc. of caustic soda solution of 34 B. are dissolved in hot water and the solution is cooled;

cc. of formaldehyde of 30% strength are then added and the whole is made up to 1 liter.

The developing bath is prepared as follows:

1 litel.

The dyeing has a bluish red shade. By preparing the grounding liquor with 2.3-hydroxynaphthoic acid 2- or ll-anisidide or 2.8-hydroxynaphthoic acid 2.5-dimethoXyl-anilide there are obtained vivid yellowish red shades.

4. 22 parts of 4 chloro-5bromo-2-amin0-1- toluene are diazotized in known manner with hydrochloric acid and sodium nitrite; the diazo solution thus obtained is introduced, while well stirring, into an aqueous suspension of 30 parts of 2.3-hydroxynaphthoic acidy-anisdide prepared by dissolving the latter in dilute caustic soda solution and reprecipitating with dilute acetic acid. The dyestuft precipitates in the form of vivid red flakes; it is filtered off after the coupling is complete, washed until neutral and advantageously used in a paste form. When dried, it is a bluish-red powder.

Similar shades and dyestuffs of very good fastness are obtained by using the diazo compounds of other bases having the general formula:

1 6 2 NH: X

wherein both the Xs stand for halogen, but at least one of which must be a bromine atom, and 2.3-hydroxynaphthoic acid-arylamides other than those indicated in the above named examples.

We claim:

1. As new products, the water-insoluble azo dyestufis of the following formula:

wherein both the Xs stand for halogen, but at least one of which must be a bromine atom and wherein the aryl residue may be substituted or not, but is to contain no free sulfonicor carboxylic groups, dyeing vivid red shades very fast to light.

2. As new products, the water-insoluble azo dyestuffs of the following formula:

O O.NH. aryl 0 O.NH. aryl wherein X stands for Cl or Br and wherein the aryl residue may be substituted or not, but is to contain no free sulfonic or carboXylic groups, dyeing vivid red shades very fast to light.

4. As new products, the water-insoluble azo dyestuifs of the following formula:

N=N 2 Br 0 O.NH.ary1

wherein the aryl residue may be substituted or not, but is to contain no free sulfonicor carboxylic groups, dyeing vivid red shades very fast to light.

5. As new products, the water insoluble azo dyestuffs of the following formula:

. Y wherein both the Xs stand for halogen, but

fast to light.

6. As new products, the water-insoluble azo wherein X stands for C1 or Br, dyeing vivid dyestuffs of the following formula: red shades very fast to light.

H30 10. As a new product, the water-insoluble l azo dyestuff of the following formula: N=N 2 3 4 5 Br H30 70 on OO.NH H300 \Y GONEO wherein X stands for C1 or Br and Y for 80 hydrogen or the OCH group, dyeing vivid red shades very fast to light.

7. As new products, the water-insoluble l m Vlvld blulsh'red shade Very fast to a llght {1Z0 dyestuffs of the i g formula" 11. Material dyed with dyestuffs as claimed 7 3 in claim 1.

2 1 5 B 12. Material dyed with dyestuffs as claimed a 4 r in claim 2. Y

O1 13. Material dyed with dyestuffs as claimed in claim 3. OH 14. Material dyed with dyestuffs as claimed H300 in claim 4:.

15. Material dyed with dyestuffs as claimed CQNH in claim 5. h 16. Material dyed with dyestuffs as claimed in claim 6. )5 wherein Y Stands for hydrogen or the 17. Material dyed with dyestuffs as claimed in claim ggg f fig dyemg red Shades Very 18. Material dyed with dyestuffs as claimed in claim 8. .23$133?!fiififilfilfafililiiifififif Magerialdyeddyestuffsasclaimed 1n 0 aim 20. Material dyed with the dyestuff as 2 1 5 X claimed in claim 10.

3 4 In testimony whereof, we aflix our signa- 40 X tures.

- RICHARD DERESER. 0H KARL MOLDAENKE.

OO H wherein both the Xs stand for halogen, but at 50 least one of which must be a bromine atom,

dyein vivid red shades very fast to light.

9. s new products, the water-insoluble azo dyestuffs of the following formula:

H30 55 G I N=N 2 5 Br 5 OCH: 

